Process for the purification of organically polluted water



May 3, 1938. o. M. URBAIN ET AL PROCESS FOR THE FUHEFICATION OF ORGANICALLY POLLUTED WATR Filed Nov. 13, 1935 3 wv @www 'WW/All @mail 55 action is expressed by equation number 5. It we rine is passed into the solution toprovide at 55 Patented May 3, 1938 UNITED STATES PATENT OFFICE PRC'ESS FOB THE PUBIFICATION 0F OBGANICALLY POLLUTED WATER Oliver M. Urbain and William R. Steinen, Co-

lumbus, Ohio, assignors to Charles 1I. Lewis, Hamster, Ohio Application November 13, 1935, Serial No. 49,614

7 Claims. (Cl. 210-2) This invention relates to a process for the puripass air through this mixture of iron and chlorine iicatlon of organically polluted water. It is the Water and the Products formed. eS eXDleSSed by purpose oi the invention to provide a process the mst iive equations, the iron is oxidized by a that can be more economically operated than different agent, namely, by the oxygen of the 5 presently employed processes; to provide a procair passed through the mixture. Thus we have 5 ess that will give markedly improved results and the iron being oxidized, as Shown in equations a process that requires a much shorter time penumbers 6 and '7. The iron oxides, shown in these riod of treatment than puriiicatlon processes curequations, are, of course, hydrated, and they Will rently employed. react with HC1 as expressed in equations num- 10 In one of its more specific aspects the invenbers 8 and 9. Equations 1, 2, 5, 6 and 7 show the 10 tion contemplates the treatment of domestic iron beine oxidized. This is most important, as sewage or the like by generating ferrie chloride it should be particularly noted that the valence in situ with accompanying oxidation of the of the iron is elevated from zero to 2, and then sewage. from 2 to 3, i. e., three complete units of valence.

Certain rather elemental reactions are availed Equation number 3 Shows the liberation of active l5 of in carrying out the process but these are em- Oxygen. e factor 0f Some importance in the Drocployed in such relationship and in such combinaeSS, aS this oxygen iS in the nascent form. tion that wholly new results are obtained.

Table o e uatz'ons To the end. that the mechanics of the process 'f q may be made clear we will refer briefly to these Equatfon NO- 1-- 2Fe+3C12-2Fec13 20 recognized reactions and then point out the ad- Equaton No- 2 FetZHClFeChiHZ vantageous manner in which they are employed Equaton No' 3-- 2HOCP` ZHCI+O2 in the pwcess Equation No. 4 Clz-i-HzOHCl-l-HOCI It has long been known that chlorine will react Equaton N 5s --nzFeChtClWzFeCh with a metal to form a salt. This reaction is ex- Equatton NO- 6 ZFGFOZ-)ZFEO 25 pressed by equation number l in the table of Equatfon No- 7 4Fe0+02 2Fe203 equations which fo110w5- Equation No. 8 FeO-l-ZHCl-FeClz-i-HzO Hydrochloric acid will react with iron to form Equatlon N0- 9 Fe2O3+6HCH2FeC13+3H2O a Salt. The reaction iS expressed by eqUtOn In this process the ferrie chloride is prepared number 2- directly in situ in the sewage and serves both as 30 Iron and iron oXideS catalyze the deC0mDOSia desolvator and as a coagulant and, as a result. tion of hypoehloious ecid- ThlS deCOmDOStiOn we obtain the many beneficial actions hereinafter is expressed by equation number 3. described,

Chlorine will attack and react With iron t0 The description of the process is simplified by form ferrie chloride. reference to the accompanying diagrammatic 35 The actions described have been employed in drawing illustrating the course of the organically the preparation of ferrie chloride. The Di'OeeSS polluted water through the treating zones. of Preparing ferrie chloride by the eetiOn 0f Referring to the drawing the general flow'of chlorine on iron is known as the Scott-Darcey the water to be treated is as follows; 40 process. It consists essentially of passing chlo- It enters at the bottom cf the oxidation tank 40 rine Water of Controlled Strength upWeld through A, overflows from the top of the oxidation tank a mass of scrap iron. Chlorine water is a soluand enters the coagulation tank B, and, after cotion which contains chlorine, hydrochloric acid agulation, enters the settling zone C. The eiiluand hypoehlorous acid. The HC1 and HOCl are ents are discharged from the zone c at D. formed by the reaction of chlorine with water. As the polluted liquid for example sewage or The reaction is expressed by equation number 4. the like passes upward in the tank A, diiused This equation iS in equilibrium only when no air is passed into the solution from the filtros HCl or HOCl is removed. When either of these plates located in the bottom of the tank. Chlorine are removed in Whole, 01' in Daft. the reaction is passed into the solution through line 2 at a proceeds to the right until equilibrium is again point just below the bed of scrap iron 3. All established. the reactions take place simultaneously within In the presence of an oxidizing mixture, such the zone occupied by the iron. Suicient air is as chlorine and HOCl, ferrous chloride (FeClz) provided to always maintain a positive oxygen is oxidized to ferrie chloride, (FeCla). The rebalance in the oxidation tank A. Suiiicient chloto complete all the reactions in this tank.

The solution next flows through line 4 and enters the coagulation zone or tank B. It is here treated with sufficient hydrated lime which is forced into the solution through line 5 at the bottom of the tank B to insure the maintenance of a pH of around pH 9.5. The material is agitated by means of a suitable agitator 6. A time period of from one to five minutes i-s suflicient for all actions occurring in the coagulation tank B.

From the coagulation zone B the material under treatment next passes through conduit 1 into the,

sedimentation tank C.

'I'his tank C may be designed along conventional lines, with proper sludge facilities, baffles, etc. A detention period of two hours in this zone is ample.

We come, now, to the reasons for the use of the agents employed in this process and the manner in which they are employed.

- The chlorine is employed to eilect the rapid oxidation of the iron with the formation of the necessary content of ferric chloride. 'I'he chlorine also sterilizes the sewage and produces in its reaction with the water some nascent oxygen, both relatively important factors. By thus accelerating the oxidation step the oxidation period for the polluted liquid is reduced to less than 30 minutes as against approximately 6 hours for the currently employed activated sludge process. The reason for this accelerated oxidation is that as the iron is being oxidized three units in valence it carries along the oxidation of the sewage constituents. The pronounced success of this process is we believe due to this discovery. The ferric chloride formed performs two functions, rst, it acts as a desolvator for the emulsoids and then the remaining excess ferrie chloride functions as a coagulant in the coagulation tank after the addition of the calcium hydroxide to raise the solution to pH 9.5. Part of the ferric chloride hydrolyzes to form an hydrous oxide which desolvates the emulsoids. In the coagulation tank sufllcient calcium chloride, (CaClz), is formed and functions as the electrolyte which ilocculates the desolvated emulsoids and other colloids. The purpose of introducing the chlorine just below the iron in the first treatment tank is to prevent the waste of chlorine in satisfying the chlorine demand of the sewage. The oxidation can be effected with atmospheric oxygen which is a much cheaper oxidizing agent than chlorine.

Among the advantages of this process may be listed the following:

1. It provides cheap and efficient method of preparing ferrie chloride in situ to act both as a desolvator and as a coagulant.

2. It permits taking advantage of the powerful oxidation set-up of chlorine plus iron, plus oxygen, plus water.

3. Iron and iron oxides catalyze the liberation of nascent oxygen from hypoch'lorous acid and this oxygen is available for the oxidation of the sewage constituents.

4. Use of air keeps the suffice of the iron free of ferrie chloride thus increasing the rate of formation of ferrie chloride.

As a further feature of our invention, we have found that soluble manganese and soluble chromium salts will catalyze the oxidation of organic polluting constituents in the presence of ferrie salts, such as ferric chloride. In our process these salts may be advantageously introduced into the oxidation tank A in a concentration of about five pounds per million gallons.

In comparing this process with the activated sludge process we find that the activated sludge process makes a reduction in B. O. D. (biochemical oxygen demand) of about 75%, B. coli about 25%, oxidation period of about 6 hours, cost of treatment from $25 to $125 per million gallons. The process of the instant invention will effect a reduction of approximately 98% in B. O. D., 100% reduction in B. colt', and has an oxidation period of around 30 minutes, and a cost of treatment not substantially exceeding $10 per million gallons treated.

What we claim as our invention is:

1. A process for the purification of organically polluted liquids comprising passing the liquid through a bed of scrap iron, introducing chlorine and diffused air to pass simultaneously with the liquid through the bed of iron forming ferrie chloride in situ, and thereafter treating the resultant liquid with hydrated lime and passing the treated liquid to a, settling zone.

2. A process for the purification of organically polluted liquid comprising subjecting the same to the simultaneous action of chlorine and diffused air in the presence of metallic iron, thereby forming ferric chloride in situ.

3. A process for the purification of organically polluted liquid comprising subjecting the same to the simultaneous action of chlorine and air in the presence of iron to form ferricchloride in situ, and thereafter raising the pH of the solution to approximately pH 9.5 and delivering the same to a suitable sedimentation zone.

4. A process for the purification of organically polluted liquid comprising subjecting the same to the simultaneous action of chlorine and air in the presence of iron to form ferrie chloride in situ, and facilitating oxidation Aof the polluting organic constituents by introducing a catalyst into the liquid simultaneously with the chiorine and the air.

5. A process for the purification of organically polluted liquid comprising subjecting the same to the simultaneous action of chlorine and air in the presence of iron to form ferric chloride in situ, and facilitating oxidation of the polluting organic constituents by introducing into the liquid simultaneously with the chlorine and the air, a catalyst, selected from the group including soluble manganese and chromium salts.

6. A process for the purification of organically polluted liquids comprising adding chlorine and diffused air to said liquid and immediately passing the mixture through a bed of scrap iron to eiect induced oxidation.

7. A process for the purification of organically polluted liquids comprising adding 'chlorine and diffused air to said liquid and passing said liquid containing chlorine and diffused air through a bed of metallic iron.

OLIVER M. URBAIN. WILLIAM R. STEMEN. 

